CN112646309B - Flame-retardant ABS plastic, preparation method thereof and application thereof in welding machine shell and electric welding auxiliary plastic tool - Google Patents
Flame-retardant ABS plastic, preparation method thereof and application thereof in welding machine shell and electric welding auxiliary plastic tool Download PDFInfo
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- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 title claims abstract description 124
- 239000003063 flame retardant Substances 0.000 title claims abstract description 124
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 title claims abstract description 118
- 238000003466 welding Methods 0.000 title claims abstract description 48
- 229920003023 plastic Polymers 0.000 title claims abstract description 25
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- 229920000647 polyepoxide Polymers 0.000 claims abstract description 39
- YSMRWXYRXBRSND-UHFFFAOYSA-N TOTP Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1C YSMRWXYRXBRSND-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000002994 raw material Substances 0.000 claims abstract description 28
- OXDXXMDEEFOVHR-CLFAGFIQSA-N (z)-n-[2-[[(z)-octadec-9-enoyl]amino]ethyl]octadec-9-enamide Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)NCCNC(=O)CCCCCCC\C=C/CCCCCCCC OXDXXMDEEFOVHR-CLFAGFIQSA-N 0.000 claims abstract description 11
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 claims description 26
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 25
- 238000002156 mixing Methods 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 13
- SWSBIGKFUOXRNJ-CVBJKYQLSA-N ethene;(z)-octadec-9-enamide Chemical compound C=C.CCCCCCCC\C=C/CCCCCCCC(N)=O.CCCCCCCC\C=C/CCCCCCCC(N)=O SWSBIGKFUOXRNJ-CVBJKYQLSA-N 0.000 claims description 12
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 11
- -1 pentabromobiphenyl ether Chemical compound 0.000 claims description 11
- 238000001125 extrusion Methods 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 6
- 238000012545 processing Methods 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
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- 229920000915 polyvinyl chloride Polymers 0.000 description 47
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- 230000000052 comparative effect Effects 0.000 description 29
- 239000011159 matrix material Substances 0.000 description 14
- 238000001514 detection method Methods 0.000 description 8
- 239000011257 shell material Substances 0.000 description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 5
- 230000008569 process Effects 0.000 description 5
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- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 description 3
- 230000009471 action Effects 0.000 description 3
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- ACRQLFSHISNWRY-UHFFFAOYSA-N 1,2,3,4,5-pentabromo-6-phenoxybenzene Chemical compound BrC1=C(Br)C(Br)=C(Br)C(Br)=C1OC1=CC=CC=C1 ACRQLFSHISNWRY-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 229910000679 solder Inorganic materials 0.000 description 2
- MXJJJAKXVVAHKI-WRBBJXAJSA-N (9z,29z)-octatriaconta-9,29-dienediamide Chemical compound NC(=O)CCCCCCC\C=C/CCCCCCCCCCCCCCCCCC\C=C/CCCCCCCC(N)=O MXJJJAKXVVAHKI-WRBBJXAJSA-N 0.000 description 1
- 241000233805 Phoenix Species 0.000 description 1
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- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
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- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical class C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 1
- 238000010891 electric arc Methods 0.000 description 1
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- 239000000945 filler Substances 0.000 description 1
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- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
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- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
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- 229920001169 thermoplastic Polymers 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L55/00—Compositions of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08L23/00 - C08L53/00
- C08L55/02—ABS [Acrylonitrile-Butadiene-Styrene] polymers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B9/00—Making granules
- B29B9/02—Making granules by dividing preformed material
- B29B9/06—Making granules by dividing preformed material in the form of filamentary material, e.g. combined with extrusion
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
Abstract
The application relates to the technical field of welding machine shells and electric welding auxiliary plastic tool materials, in particular to flame-retardant ABS plastic and a preparation method and application thereof, wherein the flame-retardant ABS plastic is prepared from the following raw materials in parts by weight: 80-130 parts of ABS resin, 15-40 parts of PVC resin, 5-15 parts of hollow glass beads, 5-15 parts of epoxy resin, 1-4 parts of flame retardant, 1-3 parts of tricresyl phosphate and 1-3 parts of ethylene bisoleamide, has the advantages of flame retardance and good impact resistance, and is mainly suitable for shells of industrial electric welding machines and auxiliary plastic tools for electric welding; in the preparation of the flame-retardant ABS plastic, a double-screw extruder is adopted to extrude a high-temperature material block, and then the material block is transferred into a single screw to be added with the hollow glass beads, the epoxy resin and other materials, so that the structural integrity of the hollow glass beads is protected to a greater extent, the excellent heat-insulating property and mechanical property of the hollow glass beads are exerted, and the flame-retardant ABS plastic with good flame retardance and impact resistance is prepared.
Description
Technical Field
The application relates to the technical field of welding machine shells and electric welding auxiliary plastic tool materials, in particular to flame-retardant ABS plastic, a preparation method and application thereof in the welding machine shells and the electric welding auxiliary plastic tools.
Background
The electric welder uses the high-temperature electric arc generated by the instantaneous short circuit of the positive and negative poles to melt the solder and the welded material on the welding electrode, so as to achieve the purpose of combining the solder and the contacted object. Because molten metal splashes are generated in the electric welding process, the shell material of the electric welding machine and auxiliary electric welding tools such as an electric welding mask and the like have the performances of insulation, impact resistance and chemical resistance and also need to have better flame retardant property so as to ensure the safety of the electric welding process.
ABS resin (Acrylonitrile-Styrene-Butadiene copolymer, ABS is the abbreviation of Acrylonitrile Butadiene Styrene) is a thermoplastic terpolymer high polymer material with high strength, good toughness and easy processing and molding. ABS resins combine the excellent properties of three monomers, namely: the ABS resin is a resin with very good comprehensive performance, has higher impact strength and surface hardness in a wider temperature range, has higher thermal deformation temperature than PA and good dimensional stability, and is widely applied to the fields of electronic appliances, instruments, machinery, automobiles, textiles, buildings and the like. At present, ABS resin is already applied to welding machine shell materials and electric welding auxiliary plastic tool materials, but the flame retardant property is poor; moreover, ABS resin can emit toxic and harmful gases such as HCN, CO and the like during combustion, so that the safety of the products in the using process is poor.
PVC resin (Polyvinyl Chloride), which is a Polyvinyl Chloride resin, is a polar non-crystalline high polymer. Unlike ABS resins, PVC resins are a flame retardant substance with "self-extinguishing" properties, and are widely used with excellent chemical stability, electrical insulation, and flame retardancy. However, PVC resin is a hard and brittle material and has poor impact resistance.
The following technical scheme is disclosed in the related art: a PVC/ABS plastic alloy material comprises the following components in percentage by mass: 20-80% of PVC resin, 3-50% of ABS resin, 1-2.3% of stabilizer, 0.3-0.9% of lubricant, 5-40% of plasticizer and 5-20% of active calcium carbonate powder. According to the related technology, the ABS resin and the PVC resin are prepared into the plastic alloy material, so that the ABS resin has the advantages of impact resistance, easiness in forming and processing and the like, and the plastic alloy material also has the flame retardance, corrosion resistance, weather resistance and scrubbing resistance of the PVC resin, and can solve the problem of poor flame retardance of pure ABS plastic products.
However, the above-described related art has the following drawbacks: 1. the PVC resin is taken as a main material, the ABS resin is taken as an auxiliary material, and although the flame retardant property of the product is better, the product has larger brittleness and poor impact resistance, and is not suitable for being applied to the shell of an industrial welding machine; 2. a large amount of PVC resin is added, PVC begins to decompose and slowly releases HCl at the temperature of more than 100 ℃, the decomposition and HCl release speed is accelerated along with the temperature rise, and more molten metal splashes exist in the electric welding process, and can cause the tool to be locally heated and heated after falling on an electric welding auxiliary tool such as a mask, more HCl is released, the stimulation is strong, and the application of the electric welding auxiliary tool in the electric welding auxiliary tool is limited.
Disclosure of Invention
Aiming at the defects in the prior art, one of the purposes of the application is to provide a flame-retardant ABS plastic which has the advantages of flame retardance and good impact resistance and can be mainly suitable for auxiliary plastic tools for electric welding.
The second purpose of the application is to provide a flame-retardant ABS plastic which has the advantages of flame retardance and good impact resistance and is mainly suitable for shells of industrial electric welding machines and auxiliary plastic tools for electric welding.
The third purpose of the application is to provide a preparation method of the flame-retardant ABS plastic with the second purpose, and the flame-retardant ABS plastic with good impact resistance and good flame retardance is prepared.
The fourth purpose of the application is to provide a preparation method of the flame-retardant ABS plastic in the optimization scheme of the second purpose, so that the flame-retardant ABS plastic with good impact resistance and good flame retardance can be prepared.
The fifth purpose of the application is to provide an application of any one of the flame-retardant ABS plastics.
The above object of the present application is achieved by the following technical solutions:
the flame-retardant ABS plastic is prepared from the following raw materials in parts by weight: 80-130 parts of ABS resin, 30-60 parts of PVC resin, 5-10 parts of epoxy resin, 3-8 parts of flame retardant, 1-3 parts of tricresyl phosphate and 1-3 parts of ethylene bis-oleamide.
By adopting the technical scheme, the ABS resin is taken as the matrix resin, the self-extinguishing PVC resin and the flame retardant are matched, and the self-extinguishing PVC resin and the flame retardant have synergistic effect, so that the flame retardant property of the product is improved under the condition of adding a relatively small amount of PVC resin; the epoxy resin and the tricresyl phosphate play a role in aging resistance; the ethylene bis-oleamide plays a role in lubrication; the ethylene bis-oleamide is cooperated with the epoxy resin and the tricresyl phosphate, so that the compatibility of the ABS resin and the PVC resin can be improved. According to the application, under the condition that the using amount of the PVC resin is relatively less, the flame retardance of the ABS resin is improved, and a product with good flame retardance and high impact strength is obtained and is suitable for auxiliary plastic tools for electric welding.
The second application object of the present application is achieved by the following technical scheme:
the flame-retardant ABS plastic is prepared from the following raw materials in parts by weight: 80-130 parts of ABS resin, 15-40 parts of PVC resin, 5-15 parts of hollow glass beads, 5-15 parts of epoxy resin, 1-4 parts of flame retardant, 1-3 parts of tricresyl phosphate and 1-3 parts of ethylene bis-oleamide.
By adopting the technical scheme, the hollow glass beads have the advantages of light weight, large volume, low heat conductivity coefficient, high compressive strength, low oil absorption rate, good dispersibility and fluidity, high chemical stability and the like. Through adding cavity glass bead in the plastics to this application, can guarantee the fire resistance of this application product when reducing PVC resin volume of mixing to can further improve the impact resistance of this application product, not only be applicable to electric welding auxiliary plastic tool, be applicable to the industry electric welding moreover.
Preferably, the method comprises the following steps: the composition is prepared from the following raw materials in parts by weight: 95-115 parts of ABS resin, 20-30 parts of PVC resin, 8-12 parts of hollow glass beads, 8-12 parts of epoxy resin, 1-4 parts of flame retardant, 1-3 parts of tricresyl phosphate and 1-3 parts of ethylene bis-oleamide.
Preferably, the method comprises the following steps: the flame retardant comprises antimony trioxide and pentabromobiphenyl ether, and the weight ratio of the antimony trioxide to the pentabromobiphenyl ether is 1: 2-4.
Through adopting above-mentioned technical scheme, through a large amount of experiments show, in this application system, the flame retardant action of adding pentabromodiphenyl ether alone to the product is greater than adding antimony trioxide alone, but adds the flame retardant action of pentabromodiphenyl ether alone to the product still less. When antimony trioxide and pentabromobiphenyl ether are compounded and used and matched with PVC resin, the flame retardant property of the plastic product is improved better.
Preferably, the method comprises the following steps: the hollow glass bead is a modified hollow glass bead processed by silane coupling agent through the following steps:
(1) drying;
(2) adding the dried hollow glass beads into a mixed solution of a silane coupling agent and absolute ethyl alcohol, uniformly stirring, filtering, taking out the hollow glass beads, and drying to obtain the hollow glass beads; the weight ratio of the silane coupling agent to the absolute ethyl alcohol is 1: 5.
By adopting the technical scheme, the hollow glass beads are inorganic fillers, and have large differences in thermal expansion coefficient, surface polarity and the like with the resin matrix, so that the hollow glass beads are poor in compatibility with the resin matrix, and direct mixing can cause the impact resistance of the plastic product to be reduced. By modifying the surface of the hollow glass bead, the interface performance and compatibility between the hollow glass bead and matrix resin are changed, and the dispersibility of the hollow glass bead in the matrix resin is improved. In the application, the hollow glass beads subjected to surface modification treatment are fully dispersed in the matrix resin, and the surfaces of the hollow glass beads are wrapped or wound with the thin resin layer, so that when the hollow glass beads are impacted by external force, the resin layer tightly wraps the hollow glass beads to prevent the hollow glass beads from sliding, and the impact resistance of the product is improved; when metal melt drips on a product, the hollow glass beads with excellent heat insulation performance have a blocking effect on heat conduction, and the flame retardant and heat resistant performance of the product is improved.
Preferably, the method comprises the following steps: the silane coupling agent is KH-550, KH-570 or KH-591.
Preferably, the method comprises the following steps: the composition is prepared from the following raw materials in parts by weight: 80-130 parts of ABS resin, 10-25 parts of PVC resin, 5-15 parts of modified hollow glass beads, 0.3-0.6 part of silane coupling agent, 5-15 parts of epoxy resin, 1-3 parts of flame retardant, 1-3 parts of tricresyl phosphate and 1-3 parts of ethylene bis-oleamide.
By adopting the technical scheme, a small amount of silane coupling agent is added into the system, so that on one hand, the flame-retardant coating has flame retardant property; on the other hand, a little excessive silane coupling agent can be inserted into the hollow glass bead filler gap wrapped with the resin layer, once the modification effect of the surface of the hollow glass bead is reduced or failed, a gap can be formed between the hollow glass bead and the resin matrix, and the excessive silane coupling agent can penetrate through the gap to be wrapped on the surface of the hollow glass bead again, so that the impact resistance and the flame retardance of the product can be further improved.
The third objective of the present application is achieved by the following technical solutions:
the preparation method of the flame-retardant ABS plastic comprises the following steps:
(1) uniformly mixing ABS resin, PVC resin, a flame retardant, tricresyl phosphate and ethylene bis-oleic acid amide, and extruding by using a double screw at the cylinder temperature of 160-170 ℃ and the neck mold temperature of 170-180 ℃ to obtain a high-temperature material block;
(2) and (3) feeding the high-temperature material block into a single-screw extruder, adding hollow glass beads and epoxy resin into a machine head at the temperature of 160 ℃ and 170 ℃ of a machine barrel and at the temperature of 170 ℃ and 180 ℃ of a neck mold, and extruding and granulating to obtain the material.
By adopting the technical scheme, in the application, the ABS resin, the PVC resin and other auxiliaries are mixed and extruded by the double screws, so that the raw materials can be uniformly mixed to obtain uniformly dispersed high-temperature material blocks; the hollow glass beads and the epoxy resin are added at the machine head, so that on one hand, the hollow glass beads can be effectively prevented from being structurally damaged when the double screws are extruded to influence the performance of the hollow glass beads, and on the other hand, the epoxy resin can be used as a 'dispersion protection layer' of the hollow glass beads, so that the hollow glass beads can be more fully and uniformly dispersed in a resin matrix, and the impact-resistant flame-retardant ABS plastic with good flame retardance can be prepared.
The fourth application purpose of the present application is achieved by the following technical solutions:
the preparation method of the flame-retardant ABS plastic comprises the following steps:
(1) uniformly mixing ABS resin, PVC resin, a flame retardant, tricresyl phosphate and ethylene bis-oleic acid amide, and extruding by using a double screw at the cylinder temperature of 160-170 ℃ and the neck mold temperature of 170-180 ℃ to obtain a high-temperature material block;
(2) and (3) feeding the high-temperature material block into a single-screw extruder, adding the modified hollow glass beads, epoxy resin and silane coupling agent into a machine head at the temperature of 160 ℃ and 170 ℃ of a machine barrel and at the temperature of 170 ℃ and 180 ℃ of a neck mold, and extruding and granulating to obtain the modified hollow glass beads.
By adopting the technical scheme, the silane coupling agent and the epoxy resin play a role in dispersing and protecting the hollow glass beads together, and the dispersion uniformity of the hollow glass beads in the matrix resin is better facilitated.
The fifth application aim of the application is realized by the following technical scheme:
the application of the flame-retardant ABS plastic of any one of the first to the fifth application aims, wherein the flame-retardant ABS plastic is used in the production and processing of a welding machine shell or/and an electric welding auxiliary plastic tool to obtain the welding machine shell or/and the electric welding auxiliary plastic tool.
In summary, the present application includes at least one of the following beneficial technical effects:
(1) the flame-retardant ABS plastic reaches V-0 of flame-retardant UL94 grade, and has excellent flame-retardant performance; the Vicat softening point and the thermal deformation temperature are both higher than those of pure ABS resin and pure PVC resin, and the flame retardant has the advantages of high temperature resistance and good flame retardant property;
(2) the tensile strength of the flame-retardant ABS plastic can reach 77 MPa; the bending strength can reach 85MPa to the maximum; the highest IZOD notch impact strength can reach 14.8 MPa; the welding rod has the advantage of impact resistance, and is suitable for production and processing of industrial welding machine shells;
(3) the flame-retardant ABS plastic has the flame-retardant property of PVC resin and the impact resistance of ABS resin; due to the synergistic effect of the hollow glass beads, the epoxy resin, the flame retardant and other materials, the flame retardant effect is ensured, the mixing amount of the PVC resin is relatively reduced, the problem of HCl release in the related technology is effectively solved, and the PVC flame retardant can be widely applied to the production and processing of the electric welding mask;
(4) in the preparation of the flame-retardant ABS plastic, a double-screw extruder is adopted to extrude a high-temperature material block, and then the material block is transferred into a single screw to be added with the hollow glass beads, the epoxy resin and other materials, so that the structural integrity of the hollow glass beads is protected to a greater extent, the excellent heat-insulating property and mechanical property of the hollow glass beads are fully exerted, and the flame-retardant ABS plastic with good flame retardance and impact resistance is prepared.
Detailed Description
The present application will be described in further detail with reference to specific examples.
The following raw materials in the application are all commercially available products, and specifically: the ABS resin is selected from Taiwan Qimei industry company, and the brand number is PA-757; the PVC resin is selected from the group consisting of Qilu petrochemical company, brand S-700; the epoxy resin is selected from Nantong star phoenix, E51, industrial grade; KH-550, KH-570 and KH-591 are analytically pure; hollow glass beads, D50 is less than or equal to 50 mu m.
Example 1
The flame-retardant ABS plastic is prepared from the following raw materials in parts by weight shown in Table 1: and uniformly mixing the dried ABS resin, the PVC resin, the flame retardant, tricresyl phosphate and ethylene bis-oleic acid amide, extruding by using double screws at the cylinder temperature of 170 ℃ and the neck mold temperature of 180 ℃, and granulating to obtain the ABS resin.
Examples 2 to 5
The flame retardant ABS plastics of examples 2-5 were prepared according to the same method as example 1, except for the differences in the types and amounts of the raw materials, as shown in Table 1.
TABLE 1 raw materials and amounts (units/g) of flame-retardant ABS plastics of examples 1 to 5
Example 6
The flame-retardant ABS plastic is prepared from the following raw materials in parts by weight shown in Table 2:
(1) uniformly mixing the dried ABS resin, PVC resin, a flame retardant, tricresyl phosphate and ethylene bis-oleic acid amide, and extruding by using double screws at the cylinder temperature of 160 ℃ and the neck mold temperature of 180 ℃ to obtain a high-temperature material block;
(2) and (3) feeding the high-temperature material block into a single-screw extruder, adding hollow glass beads and epoxy resin into a machine head at the cylinder temperature of 160 ℃ and the neck mold temperature of 180 ℃, and extruding and granulating to obtain the material.
Example 7
The flame-retardant ABS plastic is prepared from the following raw materials in parts by weight shown in Table 2:
(1) uniformly mixing the dried ABS resin, PVC resin, a flame retardant, tricresyl phosphate and ethylene bis-oleic acid amide, and extruding by using double screws at the cylinder temperature of 170 ℃ and the neck mold temperature of 170 ℃ to obtain a high-temperature material block;
(2) and (3) feeding the high-temperature material block into a single-screw extruder, adding hollow glass beads and epoxy resin into a machine head at the cylinder temperature of 170 ℃ and the neck mold temperature of 170 ℃, and extruding and granulating to obtain the hollow glass bead epoxy resin material.
Examples 8 to 13
The flame retardant ABS plastics of examples 8-13 were prepared according to the same method as in example 6, except for the differences in the types and amounts of the raw materials, as shown in Table 2.
TABLE 2 raw materials and amounts (units/g) of flame-retardant ABS plastics of examples 6 to 13
Examples 14 to 16
The flame retardant ABS plastics of examples 14-16 were prepared in the same manner as in example 12, except for the differences in the types and amounts of the raw materials, as shown in Table 3.
TABLE 3 raw materials and amounts (units/g) of flame-retardant ABS plastics of examples 14 to 16
Preparation example 1
Preparing modified hollow glass beads: drying the hollow glass beads for 1 hour at 110 ℃, and mixing absolute ethyl alcohol and a silane coupling agent KH-550 according to the mass ratio of 5:1 to obtain a mixture A for later use; and (3) uniformly mixing the dried hollow glass beads and the mixture A by adopting a high-speed stirrer at a stirring speed of 1500r/min, putting the treated hollow glass beads into an oven, and drying at 110 ℃ for 100min to obtain the hollow glass beads.
Preparation example 2
The modified hollow glass microspheres of preparation examples 2 to 3 were prepared in exactly the same manner as in preparation example 1, except that a silane coupling agent KH-570 and a silane coupling agent KH-591 were used, respectively.
Example 17
The flame-retardant ABS plastic is prepared from the following raw materials in parts by weight shown in Table 4:
(1) uniformly mixing the dried ABS resin, PVC resin, a flame retardant, tricresyl phosphate and ethylene bis-oleic acid amide, and extruding by using double screws at the cylinder temperature of 160 ℃ and the neck mold temperature of 180 ℃ to obtain a high-temperature material block;
(2) and (3) feeding the high-temperature material block into a single-screw extruder, adding hollow glass beads, epoxy resin and a silane coupling agent into a machine head at the cylinder temperature of 160 ℃ and the neck mold temperature of 180 ℃, and extruding and granulating to obtain the material.
Example 18
The flame-retardant ABS plastic is prepared from the following raw materials in parts by weight shown in Table 4:
(1) uniformly mixing the dried ABS resin, PVC resin, a flame retardant, tricresyl phosphate and ethylene bis-oleic acid amide, and extruding by using double screws at the cylinder temperature of 170 ℃ and the neck mold temperature of 170 ℃ to obtain a high-temperature material block;
(2) and (3) feeding the high-temperature material block into a single-screw extruder, adding hollow glass beads, epoxy resin and a silane coupling agent into a machine head at the cylinder temperature of 170 ℃ and the neck mold temperature of 170 ℃, and performing extrusion granulation to obtain the material.
The silane coupling agent in the flame-retardant ABS plastic raw materials of the embodiment 17 and the embodiment 18 is the same as the silane coupling agent used in the preparation of the modified hollow glass microspheres.
Examples 19 to 25
The flame-retardant ABS plastics of examples 19 to 25 differ from those of example 17 in the type and amount of raw materials, as shown in Table 4, and the rest are the same.
TABLE 4 raw materials and amounts (units/g) of flame-retardant ABS plastics of examples 17 to 25
Comparative example 1
The PVC/ABS plastic alloy material of example 1 of the related art is shown in the background art.
Comparative example 2
The ABS plastic of comparative example 2 is different from example 1 in that the flame retardant is replaced with an equal amount of PVC resin, and the rest is the same as example 1.
Comparative example 3
The ABS plastic of comparative example 3 differs from that of example 1 in that the PVC resin is replaced with the same amount of flame retardant, and the compounding ratio of antimony trioxide and pentabromobiphenyl ether in the flame retardant is the same as that of example 1, and the rest is the same as that of example 1.
Comparative example 4
The ABS plastic of comparative example 4 differs from example 1 in that: the weight ratio of antimony trioxide to pentabromobiphenyl ether in the flame retardant was 2:1, and the rest was the same as in example 1.
Comparative example 5
The ABS plastic of comparative example 5 differs from that of example 1 in that the epoxy resin is replaced with an equal amount of tricresyl phosphate, and the rest is the same as example 1.
Comparative example 6
The ABS plastic of comparative example 6 differs from that of example 1 in that tricresyl phosphate is replaced by an equal amount of epoxy resin, and the rest is the same as example 1.
Comparative example 7
The ABS plastic of comparative example 7 differs from that of example 1 in that tricresyl phosphate and epoxy resin are replaced by equal amounts of ethylenebisoleic amide, and the rest is the same as in example 1.
Comparative example 8
The ABS plastic of comparative example 8 differs from that of example 6 in that no epoxy resin is present, and is otherwise identical to that of example 6.
Comparative example 9
The flame-retardant ABS plastic is prepared from the following raw materials in parts by weight:
uniformly mixing 800g of dried ABS resin with 150g of PVC resin, 3g of antimony trioxide, 7g of pentabromobiphenyl ether, 50g of hollow glass microsphere, 50g of epoxy resin, 10g of tricresyl phosphate and 10g of ethylene bisoleic amide, and carrying out twin-screw extrusion granulation at the cylinder temperature of 160 ℃ and the die temperature of 180 ℃ to obtain the ABS resin.
Comparative example 10
The flame-retardant ABS plastic is prepared from the following raw materials in parts by weight:
uniformly mixing 1070g of dried ABS resin, 230g of PVC resin, 2.5g of antimony trioxide, 7.5g of pentabromobiphenyl ether, 50g of modified hollow glass bead of preparation example 3, 50g of epoxy resin, 3g of silane coupling agent, 13g of tricresyl phosphate and 13g of ethylene bisoleic acid amide, and carrying out twin-screw extrusion granulation at the cylinder temperature of 160 ℃ and the die temperature of 180 ℃ to obtain the ABS resin.
Performance detection
The plastics of examples 1 to 25 and comparative examples 1 to 8 were tested for their properties using the following test methods or test standards, the test results are detailed in table 5:
tensile strength (unit/MPa): ASTM D638, speed 50 mm/min;
flexural strength (unit/MPa): ASTM D790, speed 3 mm/min;
IZOD notched impact strength (unit/KJ/(m)2))：ASTM D256，3.2mm；
Vicat softening point (units/DEG C): DIN 53460 and 1976;
heat distortion temperature (Unit/. degree. C.): ASTM D638, 0.45 MPa;
flame retardancy: UL94, the flame retardant grade is gradually increased from HB, V-2, V-1 to V-0.
TABLE 5 results of property measurements of plastics of examples 1 to 25 and comparative examples 1 to 8
The detection results in Table 5 show that the flame-retardant ABS plastic of the application all reaches V-0 of flame-retardant UL94 grade, and the flame-retardant property is excellent; the tensile strength is above 47MPa, and the highest tensile strength can reach 77 MPa; the bending strength is over 62MPa, and the highest bending strength can reach 85 MPa; the IZOD notch impact strength is above 10.5MPa, and the highest IZOD notch impact strength can reach 14.8 MPa; the Vicat softening point and the thermal deformation temperature are both higher than those of pure ABS resin and pure PVC resin, and the composite material is superior to the related technology and has the advantages of impact resistance and good flame retardant property.
According to the detection results of the embodiments 1 to 5 and the embodiments 6 to 16, in the system, the addition of the hollow glass beads can not only improve the mechanical property of the flame-retardant ABS plastic, but also improve the temperature resistance and flame retardance of the flame-retardant ABS plastic. The detection results of the examples 6 to 16 and the examples 17 to 25 show that the compatibility of the hollow glass beads with the matrix resin can be effectively improved after the modification treatment is performed on the hollow glass beads, so that the mechanical property, the temperature resistance and the flame retardance of the flame-retardant ABS plastic are further improved.
According to the detection results of the comparative example 2 and the comparative example 3, in the application, the flame retardant and the PVC resin have great influence on the temperature resistance and the flame retardance of the flame-retardant ABS plastic, and the temperature resistance and the flame retardance of the product are reduced due to the absence of either of the flame retardant and the PVC resin. The test result of the comparative example 4 shows that if the addition amount of the antimony trioxide is larger than that of the pentabrominated diphenyl ether, the temperature resistance and the flame retardant property of the product are reduced. According to the detection results of the comparative example 5 and the comparative example 8, the epoxy resin has great influence on the mechanical property, the temperature resistance and the flame retardant property of the product. The detection results of the comparative examples 5 to 7 show that the epoxy resin, the tricresyl phosphate and the ethylene bis-oleic amide have a synergistic effect, and the loss of the epoxy resin or the tricresyl phosphate or both of the epoxy resin and the tricresyl phosphate can cause the reduction of the mechanical property, the temperature resistance and the flame retardant property of the product.
According to the detection results of the comparative example 9 and the comparative example 10, if all the raw materials are added into the double-screw extruder, the mechanical property of the plastic obtained after extrusion granulation is greatly reduced, the flame retardant grade is reduced from V-0 to V-1, the temperature resistance is also reduced, and the structure of the hollow glass beads is damaged during double-screw extrusion, so that the performance of the hollow glass beads is influenced. In the preparation of the flame-retardant ABS plastic, the matrix resin and the auxiliary materials are extruded by adopting double screws to obtain a high-temperature material block, and then the high-temperature material block is transferred into a single screw to be added with the hollow glass beads, the epoxy resin and other materials, so that the structural integrity of the hollow glass beads can be protected to a greater extent, the excellent heat-insulating property and the excellent mechanical property of the hollow glass beads can be fully exerted, and the flame-retardant ABS plastic with good flame retardance and impact resistance can be prepared.
In addition, the properties of the plastics of comparative example 9 and comparative example 10 are lower than those of the plastics of any of examples 1 to 5, and mainly after the structure of the hollow glass microspheres in the twin-screw extruder is destroyed, the dispersion thereof in the matrix resin is not uniform, and a case of partial stacking may occur; in addition, in the process of double-screw extrusion, the hollow glass beads are likely to slide in a larger path in the matrix resin under the action of the mechanical external force of the auger, so that more cavities are formed in the matrix resin, and the overall performance of the material is reduced.
Application example 1
The flame-retardant ABS plastic of example 4 was used in the production process of a welding mask by injection molding to obtain a welding mask.
Application example 2
The flame-retardant ABS plastic of example 12 was used in the production process of industrial welder housings by injection molding to obtain industrial welder housings.
Application example 3
The flame-retardant ABS plastic of example 22 was used in the production process of a welding mask by injection molding to obtain a welding mask.
The flame-retardant ABS plastic disclosed by the application has the flame retardant property of PVC resin and the impact resistance of ABS resin, and can meet the standard of GB4208-2017 shell protection grade when being applied to an industrial welding machine shell; due to the synergistic effect of the hollow glass beads, the epoxy resin, the flame retardant and other materials, the flame retardant effect is ensured, the mixing amount of the PVC resin is relatively reduced, the problem of HCl release in the related technology is effectively solved, and the PVC flame retardant can be widely applied to electric welding masks.
The embodiments of the present invention are preferred embodiments of the present application, and the scope of the present application is not limited by the embodiments of the present application, so: all equivalent changes made according to the structure, shape and principle of the present application shall be covered by the protection scope of the present application.
Claims (9)
1. The flame-retardant ABS plastic is characterized by being prepared from the following raw materials in parts by weight: 80-130 parts of ABS resin, 30-60 parts of PVC resin, 5-10 parts of epoxy resin, 3-8 parts of flame retardant, 1-3 parts of tricresyl phosphate and 1-3 parts of ethylene bis-oleamide; the flame retardant comprises antimony trioxide and pentabromobiphenyl ether, and the weight ratio of the antimony trioxide to the pentabromobiphenyl ether is 1: 2-4.
2. The flame-retardant ABS plastic is characterized by being prepared from the following raw materials in parts by weight: 80-130 parts of ABS resin, 15-40 parts of PVC resin, 5-15 parts of hollow glass beads, 5-15 parts of epoxy resin, 1-4 parts of flame retardant, 1-3 parts of tricresyl phosphate and 1-3 parts of ethylene bis-oleamide; the flame retardant comprises antimony trioxide and pentabromobiphenyl ether, and the weight ratio of the antimony trioxide to the pentabromobiphenyl ether is 1: 2-4; the hollow glass beads are modified hollow glass beads treated by a silane coupling agent.
3. The flame-retardant ABS plastic according to claim 2, characterized in that it is prepared from the following raw materials in parts by weight: 95-115 parts of ABS resin, 20-30 parts of PVC resin, 8-12 parts of hollow glass beads, 8-12 parts of epoxy resin, 1-4 parts of flame retardant, 1-3 parts of tricresyl phosphate and 1-3 parts of ethylene bis-oleamide.
4. The flame-retardant ABS plastic according to claim 2, wherein the hollow glass beads are modified hollow glass beads which are treated by a silane coupling agent through the following steps:
(1) drying;
(2) adding the dried hollow glass beads into a mixed solution of a silane coupling agent and absolute ethyl alcohol, uniformly stirring, filtering, taking out the hollow glass beads, and drying to obtain the hollow glass beads; the weight ratio of the silane coupling agent to the absolute ethyl alcohol is 1: 5.
5. The flame retardant ABS plastic according to claim 4, characterized in that: the silane coupling agent is KH-550, KH-570 or KH-591.
6. The flame-retardant ABS plastic is characterized by being prepared from the following raw materials in parts by weight: 80-130 parts of ABS resin, 10-25 parts of PVC resin, 5-15 parts of modified hollow glass beads, 0.3-0.6 part of silane coupling agent, 5-15 parts of epoxy resin, 1-3 parts of flame retardant, 1-3 parts of tricresyl phosphate and 1-3 parts of ethylene bis-oleamide.
7. A method for preparing the flame-retardant ABS plastic as claimed in any of claims 2 to 5, which is characterized in that the flame-retardant ABS plastic is prepared by the following steps:
(1) uniformly mixing ABS resin, PVC resin, a flame retardant, tricresyl phosphate and ethylene bis-oleic acid amide, and extruding by using a double screw at the cylinder temperature of 160-170 ℃ and the neck mold temperature of 170-180 ℃ to obtain a high-temperature material block;
(2) and (3) feeding the high-temperature material block into a single-screw extruder, adding the modified hollow glass beads and epoxy resin into a machine head at the temperature of 160 ℃ plus 170 ℃ and the temperature of a neck mold at the temperature of 170 ℃ plus 180 ℃, and performing extrusion granulation to obtain the modified hollow glass beads.
8. The preparation method of the flame-retardant ABS plastic as recited in claim 6, which is characterized by comprising the following steps:
(1) uniformly mixing ABS resin, PVC resin, a flame retardant, tricresyl phosphate and ethylene bis-oleic acid amide, and extruding by using a double screw at the cylinder temperature of 160-170 ℃ and the neck mold temperature of 170-180 ℃ to obtain a high-temperature material block;
(2) and (3) feeding the high-temperature material block into a single-screw extruder, adding the modified hollow glass beads, epoxy resin and silane coupling agent into a machine head at the temperature of 160 ℃ and 170 ℃ of a machine barrel and at the temperature of 170 ℃ and 180 ℃ of a neck mold, and extruding and granulating to obtain the modified hollow glass beads.
9. Use of a flame-retardant ABS plastic according to one of claims 1 to 6, characterized in that: the flame-retardant ABS plastic is used in the production and processing of a welding machine shell or/and an electric welding auxiliary plastic tool to obtain the welding machine shell or/and the electric welding auxiliary plastic tool.
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